Process for breaking petroleum emulsions



Patented Mar. 28, 1944 attests PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, pniversimpit and Keiser, Webster Groves, Ma, assignorsto rolite Corporation, Ltd Wilmington, Del., a

corporation of Delaware No Drawing. Application May 25, 1942,

senam srasm v 9 Claims. (ma-336) 7 This invention relates primarily to the resolution of petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil," roily .oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. Another object is. to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The compounds used as the demulsifing agent of our process, are the oxyalkylation products derived by the oxyalkylation' of compounds sometimes referred to as "acidyl-aryl-sulphonimids. (See U. S. Patent No. 1,145,499, dated July 15, 1915 to Biickel.) Such sulphonimids represent the product obtained by the introduction of two acyl radicals into the ammonium radical, one acyl radical being derived from a high molal detergent-forming monocarboxy acid, and the other acyl radical being derived from an aryl sulfonic acid. Since the word acyl can properly be employed to describe both such acidic radicals, it is convenient to use the word acidyl in a limited sense to refer to the acyl radical derived from a carboxy acid.

The expression detergent-forming monocarboxy acids" has been frequently employed in the literatureto designate certain high molal acids having at least 8 and not more than 32 carbon marine sources. Other well-known examples inx elude resinic acids, such as abietie acid, naturalacid. For instance, chlorinated oleic acid will serve as satisfactorily as oleic acid. Hydrogenated-abietic acid is as satisfactory as the material prior to hydrogenation. Brominated naphthenic acid is as satisfactory as the naphthenic acid itself. This also applies to similar derivatives obtainable from oxidized petroleum acids, wax acids, etc.

The aryl group may be-monocylic or polycyclic. In the polycyclic type the rings may be separated or fused. One or' more alkyl radicals may be substituted in aromatic nucleus, for instance,

derivatives may be obtained from toluene, xylene,

' acted with ammonia to yield the sulphonamid.

ly-occurring petroleum acids such as those obtalned by the oxidation of petroleum hydrocarbons, waxes and the like, and form certain naturally-occurring waxes. Such monocarboxy detergent-forming acids may be cyclic or acyclic. They may be saturated or unsaturated. Included also are derivatives which do not eliminate the soap-forming property and which are obviously chemical equivalents of the unmodified phonchlorides depends uponreaction with the corresponding sulfonic acid, certain non-metallic halides, such as sulphurehlorides, or phosphorous chlorides being employed. numerous substitutedaromatic sulfonic acids in the manner described in U. S. Patent No. 2,278,167, dated March 31, 1942, to De Groote and Keiser. It is, of course, understood that unsubstituted aromatic sulfonic acids may be employed, and in fact, in some instances are available as inexpensive by-products. The manufacture of the acyl chlorides presents no particular difliculty, especially when manufactured fromv high molal saturated monocarboxy acids. Reference is made to the manufacture from saturated fatty acids, from naphthenic acids, wax acids obtained from naturally-occurring waxes, oxidized petroleum acids, etc. Some of the procedures employed for preparing the high molal acyl chlorides are not as satisfactory when unsaturated acids such as oleic acids are employed.

One can prepare ,Thus, sulphurchloride may serve satisfactorily for preparing the acyl chloride from stearic acid, but is not as satisfactory, if oleic acid is used. Phosphorous chlorides, for instance, phosphorous pentachloride, may be used equally satisfactorily, as a rule, with either saturated acids, or monoethylenic acids. The same is true of thionyl chloride. As to such procedures, see aforementioned Biickel patent. When the high molal acids are of the polyethylenic type, or contain some other functional group, in .addition to a single ethylene linkage, other difiiculties may be encountered and special methods may be required.

When a sulphonamid, particularly a m'onocyclic sulphonamid free from nuclear substituted alkyl radicals, or having, at the most, short chain alkyl radicals present, is treated with suitable acidyl chloride, one obtains practically a quantitative yield of the acidyl-aryl-sulphonimid. This procedure is so simple that it may be readily illustrated by the procedure described in the aforementioned Biickel patent. The short alkyl I chain or chains preferably have less than 6 carbon atoms.

AomYL-ARYL-Smrnomum Example 1 98 kilos of' sodium. benzenesulfonamid are heated .in an oil bath for about 1-2 hours at about IOU-420 0., with 152 kilos of stearic acid chlorid. When recrystallized from alcohol, the crude product melts at 104 C.

ACmYL-AnYL-SULrI-IomMIn Example 2 in which R1, R2, and R3 represent hydrogen atoms or alkyl radicals containing one to twenty carbon atoms. R is an aromatic nucleus of ,the monocyclic or polycyclic type, and R is an acidyl radical obtained from a high molal detergentforming monocarboxy acid-having at least 8 carbon atoms and, not more than 32 carbon atoms.

We have found that if an acidyl-aryl-sulphonimid of the kind above described is treated with-{an oxyalkylating agent in the customary manner employed to oxyalkylate a phenol, a

high molal acid, or the like, one obtains a variety of valuable compounds which may be water-insoluble, or water-miscible, or water-soluble, de-

kalies to give salts. Cofirpare'with the well-known -Hinsberg reaction. Thus essentially, the same procedure may be employed in oxyalkylation as 76 "imid acidic. Such compounds combine with al-- is used in the treatment of high'molal sulfonic acids. For instance, see U. S. Patent No; 2,208,- 581, dated July 23, 1940, to Hoeifelmann. Briefly stated, the procedure employed is to treat the anhydrous sulphonamid with a suitable alkylating agent containing a reactive ethylene oxide ring. As typical examples of applicable com-pounds may be mentioned glycerine epichlorhydrin, gly-.

cide alcohol, ethylene oxide, propylene oxide, bu -tene'-2-oxide, butene-l-oxide, isobutylene oxide,

' acid, polybasic acids, such as maleic acid, phthalic-acid, etc. If a comparatively larger proportion of oxyalkylating agent per mole of sulphonimid is employed, forinstance, 5 to 10 moles of ethylene oxide, the hydrotropic property and hydrophile property. are greatly enhanced. If 20-60 moles of the oxyalkylating agent, particularly ethylene oxide, is employed, one may obtain water-solubility, provided that the molal weight of the initial sulphonimid is not too'large. Generally speaking, a minimum of two moles of ethylene oxide must be introduced for each carbon atom in the:sulphonamid. Sometimes a smaller amount can be employed to obtain water- .solubility, where, in other instances, as many as four moles per mole of carbon atom mustf be introduced. I

Considering momentarily compounds derived from ethylene oxide, they may be depicted in the following manner:

in which all the characters have their previous significance and. 1!. may represent any number from 1 to-60.

In view of what has been said, it hardly appears necessary to include examples beyond stating that oxyalkylation can generally be conducted under mild conditions of reaction. For instance, a temperature of -125 C. is usually satisfactory; secondly, pressure of less than 200 pounds pen, square inch gauge pressure is usually satisfactory, the reaction may take place in a comparatively short period, for instance, two hours or less, but in other instances as long as twenty hours-may be employed. The reaction is conducted by using a suitable apparatus that insures intimate contact between the oxyalkylating agent and the sulphonimid. After the introduction of the first molecule of ethylene oxide or oxyalkylating agent, acidity has disappeared, and the subsequent stages are sometimes suitably catalyzed by the presence of a small amount of alkali, such as caustic soda, sodium methylate, soap, or the like, which may be present to the extent of one tenth of,1% to one-half of',1%. Compare with the oxyalkylation of highnnolal alcohols.

' such as benzene,

Oxnnxrmrsn ACIDYL-ARYL-SULPHONIMID Example 1 OXYALKYLATED ACIDYL- ARYL-SULPHONIMID Emample 2 The substituted i-mid obtained in the manner described in the preceding example is mixed with two tenths of 1% of sodium methylate and then subjected to further oxyethylation with 5 pound moles of ethylene oxide for each pound mole of the substituted imid.

OXYAIJKYLATED ACIDYL-ARYL-SULPHONIMID Example 3 The same procedure is followed as in the preceding example, except that 10-20 pound moles of ethylene oxide are used for each pound mole of the substituted imid.

OXYALKYLATED AcinYL-ARYL-SuLP'HoNmm Example 4 Palmityl paratoluene sulphonimid obtained in the manner previously described, is substituted for stearyl benzene sulphonimid in Examples 1-3, preceding.

OxvALxYLA'rnn AcInYL-ARYL-SoilPHomMIn Example 5 The same procedure is followed as in Exam ples 1-3, preceding, except that the sulphonimid is derived from mixed high molal fatty acid chlorides of the kind available in the open market, and the sulphonimid is derived from cymene.

As has been suggested, one need not employ the sulphonimid derived from a single fatty acid, but one may employ the imid derived from a mixture of fatty acids, and especially, from the mixture obtained by the hydrogenation of naturally Occurring fats or oils. For instance, unsaturated naturally occurring oils, such as olive oil, teaseedoil, soyabean oil, cottonseed oil, etc., may be hydrogenated and then subjected to saponification or hydrolysis. The mixture of fatty acids so ob tained or the mixture obtained from palm oil, or palm kernel oil, may be converted into a corresponding acyl chloride and employed in the present instance. Attention is again directed to the fact that it is our preference to use an oxyalkylating agent having not over 4 carbon atoms, 1. e.,

ethylene oxide, propylene oxide, butylene oxide, glycidol, and methyl glycidol.

Conventional demulsifying agents employed in I the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, toluene, xylene, tar acid oil, cresol, anthracene oi1,-et0.'. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl 'ventional demulsifying a ents.

alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents,-

such as pine oil, carbon tetrachloride, sulfur dioxide extract obtaine inthe refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials herein described may be admixed with one or more of the solvents customarily used in connection with cone Moreover, said material or materials may be used alone, or in admixture with other suitable well-known classes of demulslfying agents.

It is well known that conventional demulsifying agentsmay be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials herein described. I

We desire to point out that the superiority of the reagent or demulsifying agent employed in our herein described process for breaking petroleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available. a

In practising our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above pro cedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a, demulsifying agent comprising an oxyalkylated derivative of an acidyl-aryl-sulphonimid of the formula: H

resom i in which R is an aromatic nucleus, and R is an acidyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 82 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reac- 6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a. demulsifying agent comprising an oxyalkylated derivative of an acidyl-aryl-sulphonimid or the formuia:

R.SO:.N

R! in which R is a monocyclic aromatic nucleus having at least 1 alkyl side chain containing less tive ethylene oxide ring; said'oxyalkylating agent having not more than 4 carbon atoms.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsitying agent comprising an oxyalkylated derivative of an acidyl-aryl-sulphonimid of the formula:

n asom I in which R. is an aromatic nucleus having at least 1 alkyl side chain containing less than 6 carbon atoms, and-R is an acidyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms; said derivative being obtained by means of an oiwalkylating agent having a reactive ethylene oxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

4. A process for breaking petroleum emulsions of the water-in-oii type, characterized .by subjecting the emulsion to the actionof a demulsitying agent comprising an oxyalkylated derivative of an acidyl-aryl-sulphonimid of the formula:

11 RBOLN/ R! in which R is a monocyclic aromatic nucleus having at least 1 al yl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsifying agent comprising an oxyalkylated derivativfl or an acidyi-aryl-sulphonimid of the form a:

6 carbon atoms, and R is .an acidyl radical obtained from a higher fatty acid having at least 8 and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

than 6 carbon atoms, and R is an acidyl radical obtained from an unsaturated higher fatty acid having at least 8 and not more than 32 carbon atoms; said derivative being obtained by means 01' an oxyalkylating agent having a reactive ethyleneoxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action oi. a demulsifying agent comprising an oxyethylated derivative of an acidyl-aryl-sulphonimid oi the formula:

in which R is a monocyclic aromatic nucleus having at least one-alkyl side chain containing less than six carbon atoms, and R is; an acidyl radical: obtained from an unsaturated higher fatty acid having at least 8 and not more than 32 carbonatoms; said oxyethylated derivative being of the water-insoluble type.

8. g A process for breaking petroleum emulsions of the water-in-oil type, characterized bysub- 'iecting the emulsion to the action or a demulsifying agent comprising an oxyethylated derivative ofan acidyl-aryl-sulphonimid oi the formula:

in which R is a monocyclic aromatic nucleus having at least one alkylside chain containing less than 6 carbon atoms, and-R is an acidyl radical obtained from an unsaturated higherfatty acid having at least 8 and not more than 32 carbon atoms; said oxyethylated derivative being of the water-miscible type.

9. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub-'- jecting the emulsion to the action of a demulsitying agent comprising an oxyethylated derivative of an acidyl-aryl-sulphonimid of the Jarmula:

in which R is a monocyclic aromatic nucleus having at least one alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from an unsaturated higher fatty acid having at least 8 and not more than 32 carbon atoms; said oxyethylated derivative being of the water-soluble type.

- MELVIN DE GROOTE.

BERNHARD 

